JP5260538B2 - Preparation procedure for purified cationic guar - Google Patents
Preparation procedure for purified cationic guar Download PDFInfo
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- JP5260538B2 JP5260538B2 JP2009536678A JP2009536678A JP5260538B2 JP 5260538 B2 JP5260538 B2 JP 5260538B2 JP 2009536678 A JP2009536678 A JP 2009536678A JP 2009536678 A JP2009536678 A JP 2009536678A JP 5260538 B2 JP5260538 B2 JP 5260538B2
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- 244000007835 Cyamopsis tetragonoloba Species 0.000 title claims description 57
- 125000002091 cationic group Chemical group 0.000 title claims description 48
- 238000000034 method Methods 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 239000008186 active pharmaceutical agent Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 20
- 239000002537 cosmetic Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- 238000009472 formulation Methods 0.000 description 8
- 230000003750 conditioning effect Effects 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 101150016253 cmr2 gene Proteins 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 4
- -1 Cationic polysaccharides Chemical class 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 101150100788 cmr3 gene Proteins 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002453 shampoo Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- FBPHYBUFTJVHCG-UHFFFAOYSA-N 1-propoxypropane;hydrochloride Chemical compound Cl.CCCOCCC FBPHYBUFTJVHCG-UHFFFAOYSA-N 0.000 description 2
- 101100350964 Arabidopsis thaliana PANS1 gene Proteins 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101150076566 CMR1 gene Proteins 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 101100047461 Rattus norvegicus Trpm8 gene Proteins 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000000118 hair dye Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YSRQRFIVCMIJJE-UHFFFAOYSA-M 2,3-dihydroxypropyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)CO YSRQRFIVCMIJJE-UHFFFAOYSA-M 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- OSCJHTSDLYVCQC-UHFFFAOYSA-N 2-ethylhexyl 4-[[4-[4-(tert-butylcarbamoyl)anilino]-6-[4-(2-ethylhexoxycarbonyl)anilino]-1,3,5-triazin-2-yl]amino]benzoate Chemical compound C1=CC(C(=O)OCC(CC)CCCC)=CC=C1NC1=NC(NC=2C=CC(=CC=2)C(=O)NC(C)(C)C)=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=N1 OSCJHTSDLYVCQC-UHFFFAOYSA-N 0.000 description 1
- OYINQIKIQCNQOX-UHFFFAOYSA-M 2-hydroxybutyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCC(O)C[N+](C)(C)C OYINQIKIQCNQOX-UHFFFAOYSA-M 0.000 description 1
- VLRGXXKFHVJQOL-UHFFFAOYSA-N 3-chloropentane-2,4-dione Chemical compound CC(=O)C(Cl)C(C)=O VLRGXXKFHVJQOL-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 206010019049 Hair texture abnormal Diseases 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 206010074268 Reproductive toxicity Diseases 0.000 description 1
- 206010040844 Skin exfoliation Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- XIVLWOXCLOIZSW-UHFFFAOYSA-M chloromethyl-(2-hydroxypropyl)-dimethylazanium;chloride Chemical compound [Cl-].CC(O)C[N+](C)(C)CCl XIVLWOXCLOIZSW-UHFFFAOYSA-M 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000003766 combability Effects 0.000 description 1
- 239000008406 cosmetic ingredient Substances 0.000 description 1
- 230000035618 desquamation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 231100000091 reproductive toxicant Toxicity 0.000 description 1
- 231100000372 reproductive toxicity Toxicity 0.000 description 1
- 230000007696 reproductive toxicity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000723 toxicological property Toxicity 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
- C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Cosmetics (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
本発明は、ホウ素を含有せず、化粧品分野および家庭用洗浄製品における使用に適した、精製カチオン性グアー（purified cationic guar）の調製手順に関する。 The present invention relates to a procedure for the preparation of purified cationic guar, which does not contain boron and is suitable for use in the cosmetic field and household cleaning products.
本発明の手順によって得られるカチオン性グアーは、酸性および塩基性ｐＨの両方で水に可溶であり、したがって、極めて広い幅のｐＨを有する水溶液において粘性を発現するという技術的に有用な特性を有している。さらに、上記カチオン性グアーはそれを化粧品分野に適したものとする純度を有する。 The cationic guar obtained by the procedure of the present invention is soluble in water at both acidic and basic pH, and thus has the technically useful property of developing viscosity in aqueous solutions having a very wide pH range. Have. Furthermore, the cationic guar has a purity that makes it suitable for the cosmetic field.
カチオン性多糖類は天然由来の誘導体であり、そのコンディショニング特性により、工業的な添加剤として多用されている（すなわち、これらは、これらが適用される基材、一般的には紙、皮膚、髪または布（fabric）の特性を改善する）。 Cationic polysaccharides are naturally derived derivatives that are widely used as industrial additives because of their conditioning properties (ie they are the substrates to which they are applied, typically paper, skin, hair. Or improve the properties of the fabric).
この特性は、これらを、シャンプー、ヘアコンディショナー、クリーム、パーソナルケアまたはハウスホールドケア洗浄剤、および、布にソフトな肌触りと帯電防止性を付与する軟化剤の調製のために、産業上有用なものとする（例えばConditioning Agents for Hair & Skin, Ed. R. Schueller and P. Romanowski, Marcel Dekker Inc, NY, 1999を参照）。 This property makes them industrially useful for the preparation of shampoos, hair conditioners, creams, personal care or household care cleaners, and softeners that impart soft touch and antistatic properties to the fabric. (See, for example, Conditioning Agents for Hair & Skin, Ed. R. Schueller and P. Romanowski, Marcel Dekker Inc, NY, 1999).
そのコンディショニング能力のほか、これらの多糖類の、これらが溶解された溶液を増粘し、そのレオロジーを調整する能力は産業上有用である。 In addition to its conditioning ability, the ability of these polysaccharides to thicken the solution in which they are dissolved and adjust their rheology is industrially useful.
特に、カチオン性ポリガラクトマンナン、中でもグアーガムのカチオン性誘導体は、これらが調合されたシャンプーで洗浄した髪の湿潤時および乾燥時の櫛通り性（combability）の改善について最適な結果を示している。 In particular, cationic polygalactomannans, especially cationic derivatives of guar gum, have shown optimal results in improving the combability of wet and dry hair washed with shampoos in which they are formulated.
化粧用調合物（cosmetic formulation）において、明確に加えられたものでも制御されたものでもなく、予測されたものでもなく、バッチごとに変化し得る物質の存在が、例えわずかな量であっても、前記調合物の調製中に、相分離や粘度の変動などの問題を生じさせ得ることはよく知られている。 In cosmetic formulations, neither explicitly added nor controlled, nor anticipated, the presence of substances that can change from batch to batch, even in small quantities It is well known that problems such as phase separation and viscosity fluctuations can occur during the preparation of the formulation.
さらに、ここ数年の間に、化粧品の製造に用いる原材料の毒性に特別の注意が払われるようになった。例えば、ＥＣ指令７６／７６８／ＥＥＣおよびその後の改訂は、消費者の健康を守る目的で、化粧品用の原料における特定の物質の存在を制限するか、禁止している。 Furthermore, during the last few years, special attention has been paid to the toxicity of the raw materials used in the production of cosmetics. For example, EC Directive 76/768 / EEC and subsequent revisions limit or prohibit the presence of certain substances in cosmetic ingredients for the purpose of protecting consumer health.
特に、上記指令は、ＥＥＣ指令６７／５４８／ＥＥＣによる付属書ＩＩに列挙され、発がん性、変異原性または生殖毒性として分類されている、カテゴリーＣＭＲ１、ＣＭＲ２またはＣＭＲ３に関する複数の物質の化粧品における存在を禁止している。同じＥＣ指令７６／７６８／ＥＥＣによれば、必ずしも成分として存在しないが、原材料の生産過程に由来する不純物としてのみ存在する他の物質（付属書ＩＩＩに列挙された物質）の存在は、量的制限の対象となっている。 In particular, the Directive is listed in Appendix II by EEC Directive 67/548 / EEC and presents in cosmetics a plurality of substances relating to categories CMR1, CMR2 or CMR3, classified as carcinogenic, mutagenic or reproductive toxic. Is prohibited. According to the same EC Directive 76/768 / EEC, the presence of other substances (substances listed in Annex III) that are not necessarily present as components but are present only as impurities from the raw material production process is quantitative It is subject to restrictions.
したがって、化粧用調合物、および、皮膚と直接接触する調合物、例えば、家庭用洗浄製品などに用いるには、消費者の健康のため、および化粧品の製造に関連する技術的問題のために、グアーのカチオン性誘導体が不純物を可能な限り有しないことが根本的に重要である。 Therefore, for use in cosmetic formulations and formulations that come into direct contact with the skin, such as household cleaning products, for consumer health and due to technical problems associated with the manufacture of cosmetics, It is fundamentally important that the cationic derivatives of guar have as little impurities as possible.
さらに、化粧用調合物または家庭用洗浄剤のｐＨは、落屑防止剤の明らかに酸性のｐＨから染髪料の明らかに塩基性のｐＨまで多種多様である。したがって、これらの製品には、あらゆるｐＨにおいて水に可溶な成分を用いるのが産業上好都合である。 Furthermore, the pH of cosmetic preparations or household cleaners varies widely from the apparently acidic pH of desquamation inhibitors to the apparently basic pH of hair dyes. Therefore, it is industrially convenient for these products to use components that are soluble in water at any pH.
カチオン性グアー誘導体は、その使用が防水紙の製造において言及された７０年代初頭から知られている（US 3,589,978参照）。 Cationic guar derivatives have been known since the early 70's when their use was mentioned in the manufacture of waterproof paper (see US 3,589,978).
カチオン性グアー誘導体の化粧品における最初の使用は、グアーのカチオン性誘導体が、通常の洗浄力のほかにヘアコンディショニング特性を有する、いわゆる「ツーインワン」シャンプーの製造に使用された１９７７年に遡る（US 4,061,602参照）。 The first use of cationic guar derivatives in cosmetics dates back to 1977 when the guar cationic derivatives were used to make so-called “two-in-one” shampoos, which have hair conditioning properties in addition to the usual detergency (US 4,061,602). reference).
化粧品に用いられるカチオン性グアー誘導体は、グアーヒドロキシプロピルトリモニウムクロリドのＩＮＣＩ名で知られており、化学的にはグアー２−ヒドロキシ−３−（トリメチルアンモニウム）プロピルエーテルクロリドである。 Cationic guar derivatives used in cosmetics are known by the INCI name of guar hydroxypropyltrimonium chloride and are chemically guar 2-hydroxy-3- (trimethylammonium) propyl ether chloride.
その合成は、例えば、引用したUS 3,589,978特許に記載されているように、塩基性触媒（水酸化ナトリウムなど）の存在下での、２，３−エポキシプロピルトリメチルアンモニウムクロリドまたは（３−クロロ−２−ヒドロキシプロピル）トリメチルアンモニウムクロリドの、グアーのヒドロキシル基に対する反応を必要とする。 Its synthesis is described in, for example, 2,3-epoxypropyltrimethylammonium chloride or (3-chloro-2, in the presence of a basic catalyst (such as sodium hydroxide) as described in the cited US 3,589,978 patent. Requires reaction of -hydroxypropyl) trimethylammonium chloride to the hydroxyl group of guar.
試薬２，３−エポキシプロピルトリメチルアンモニウムクロリドは、発がん物質ＣＭＲ２として分類される。試薬３−クロロ−２−ヒドロキシプロピルトリメチルアンモニウムクロリドは、対応するエポキシドより毒性は低いとしても、ＣＭＲ３に分類され、アルカリ媒体中で２，３−エポキシプロピルトリメチルアンモニウムクロリドに変換される。 The reagent 2,3-epoxypropyltrimethylammonium chloride is classified as a carcinogen CMR2. The reagent 3-chloro-2-hydroxypropyltrimethylammonium chloride is classified as CMR3 even though it is less toxic than the corresponding epoxide and is converted to 2,3-epoxypropyltrimethylammonium chloride in an alkaline medium.
US 3,589,978に記載されているところによると、反応はイソプロパノール、メタノール、エタノールおよびｔｅｒｔ−ブタノールなどの溶媒中、３０〜６０℃の温度で行うことができる。同特許の例Ａにおいて、反応の終わり、および、アルカリ過剰の中和の後、未反応の４級試薬を除去すべく、生成物を乾燥し、粉砕し、メタノールで洗浄する。 According to US 3,589,978, the reaction can be carried out in a solvent such as isopropanol, methanol, ethanol and tert-butanol at a temperature of 30-60 ° C. In Example A of the same patent, after the reaction and neutralization with excess alkali, the product is dried, ground and washed with methanol to remove unreacted quaternary reagents.
US 3,589,978には、最終生成物中のカチオン試薬（２，３−エポキシプロピルトリメチルアンモニウムクロリド）の残留量について何ら報告されていないが、メタノールはそれ自体毒性物質であると見ることができる。 US 3,589,978 does not report any residual amount of cationic reagent (2,3-epoxypropyltrimethylammonium chloride) in the final product, but methanol itself can be viewed as a toxic substance.
US 4,031,307には、塩基性触媒を含む水と水溶性溶媒との混合物中で固形グアーとカチオン化試薬とを反応させることによる、二相系におけるグアーのカチオン性誘導体の調製が記載されている。反応の後、得られた生成物は、遠心またはろ過によって分離し、好ましくは、合成に用いた水−溶媒混合物による第１の洗浄と、同じ溶媒のより無水の形態による第２の洗浄とにより精製する。 US 4,031,307 describes the preparation of a cationic derivative of guar in a two-phase system by reacting solid guar with a cationizing reagent in a mixture of water and a water-soluble solvent containing a basic catalyst. After the reaction, the product obtained is separated by centrifugation or filtration, preferably by a first wash with the water-solvent mixture used for the synthesis and a second wash with a more anhydrous form of the same solvent. Purify.
US 2001051143には、反応の終わりに８５重量％のイソプロパノール水溶液による第１の洗浄と、純粋なイソプロパノールによる第２の洗浄とを含む、グアーのカチオン性誘導体の調製が記載されている。US 2001051140には、反応の終わりに、８５％イソプロパノール水溶液による２回の洗浄を含む、グアーのカチオン性誘導体の調製が記載されている。 US 2001051143 describes the preparation of a cationic derivative of guar comprising a first wash with 85% by weight aqueous isopropanol at the end of the reaction and a second wash with pure isopropanol. US 2001051140 describes the preparation of a cationic derivative of guar comprising two washes with 85% aqueous isopropanol at the end of the reaction.
これらの刊行物のいずれにおいても、得られたカチオン性グアー誘導体に存在する不純物の種類や量は言及されていない。この不純物は、カチオン性グアー誘導体が化粧用原材料として用いられる場合に、最終的な化粧品の一部になるものである。 None of these publications mentions the type or amount of impurities present in the resulting cationic guar derivative. This impurity is part of the final cosmetic product when the cationic guar derivative is used as a cosmetic raw material.
現在市販されているカチオン性グアー誘導体の大部分は、水および溶媒での洗浄による精製に関連する困難性および負担を回避するため、例えばCA 2,023,324に記載のように、事前にホウ酸塩で架橋した生成物を水のみで洗浄することにより精製されており、反応相にはホウ砂が添加されている。こうして得られるカチオン性グアー誘導体は、少量のホウ素を含む（ホウ酸化（borated）グアー）。 The majority of currently marketed cationic guar derivatives are pre-cross-linked with borate to avoid the difficulties and burdens associated with purification by washing with water and solvents, for example as described in CA 2,023,324. The product thus obtained is purified by washing only with water, and borax is added to the reaction phase. The cationic guar derivative thus obtained contains a small amount of boron (borated guar).
ホウ酸による架橋の目的は、ホウ酸アニオンを介して多糖鎖の間に結合を形成し、生成物を水に不溶性にすることである。
これらの結合は塩基性ｐＨで安定しており、したがって、かかる条件では、生成物を副産物から洗い出すことができる。
酸性条件ではホウ酸塩による結合が取り除かれ、生成物は可溶であり、その増粘およびコンディショニング特性を発揮することができる。
The purpose of crosslinking with boric acid is to form bonds between the polysaccharide chains via borate anions, making the product insoluble in water.
These linkages are stable at basic pH, so that under such conditions, the product can be washed out from the byproduct.
In acidic conditions, the borate linkages are removed and the product is soluble and can exhibit its thickening and conditioning properties.
ホウ酸塩による反応は、ｐＨ変化により可逆的である。したがって、生成物が酸性のｐＨで予め可溶化されていたとしても、それをアルカリ条件に戻すことにより、調合物の粘性を変化させ、その結果、製品の質を変えることができる。 The borate reaction is reversible with pH changes. Thus, even if the product has been previously solubilized at an acidic pH, returning it to alkaline conditions can change the viscosity of the formulation and, consequently, the product quality.
したがって、ホウ酸化カチオン性グアー誘導体の限界は、ホウ酸塩で処理した生成物が７を超えるｐＨで可溶ではないため、酸性または弱酸性ｐＨで使用される製品にしか適用できないことである。
さらにまた、ホウ酸誘導体がカテゴリーＣＭＲ２の生殖毒性物質として分類されていることを認識しなければならない。
Thus, the limitation of borated cationic guar derivatives is that they can only be applied to products used at acidic or weakly acidic pH because the borate treated product is not soluble at pH above 7.
Furthermore, it should be recognized that boric acid derivatives are classified as category CMR2 reproductive toxicants.
染髪料は、最も大きく拡大しているホームおよびパーソナルケア分野の１つである。これらは通常、８を超えるｐＨで調合され、したがって、これらにホウ酸での架橋により精製したカチオン性グアー誘導体を調合することはできない。 Hair dyes are one of the most expanding areas of home and personal care. They are usually formulated at a pH above 8, and therefore they cannot be formulated with cationic guar derivatives purified by crosslinking with boric acid.
一般的に水溶液中で７．５を超えるｐＨを有し、通常皮膚用の軟化剤およびコンディショニング剤を含有する固形石鹸バーの調製は、非ホウ酸化カチオン性グアー誘導体の使用に関して大いに関心を集めている別の分野である。 The preparation of bar soap bars, generally having a pH above 7.5 in aqueous solution and usually containing skin softeners and conditioning agents, has attracted much interest regarding the use of non-borated cationic guar derivatives. Is another area.
一般に塩基性ｐＨを有し、場合によっては皮膚保護機能を有する共調合剤（co-formulating agent）を有利に含有する脱毛クリームの調製および布用粉末洗浄剤の生産は、非ホウ酸化カチオン性グアー誘導体を用いることができるさらなる調合物である。 The preparation of a hair removal cream and the production of a powder cleaning agent for fabrics, which advantageously contains a co-formulating agent which has a basic pH and in some cases has a skin protection function, is a non-borated cationic guar. Further formulations in which derivatives can be used.
出願人は今回、あらゆるｐＨで可溶であり、ホウ素を含まず、それが成分として用いられる化粧用調合物の安定性または毒性学的特性に影響し得る他の不純物の含量が少ない、精製カチオン性グアーの調製手順を見出した。 Applicants now have purified cations that are soluble at any pH, free of boron, and low in other impurities that can affect the stability or toxicological properties of the cosmetic formulation used as an ingredient. A procedure for preparing sex guar was found.
したがって、本発明の基本的な対象は、以下の工程：ａ）１００重量部のグアー粉を、２０〜５０重量％の水を含有する５〜５００重量部の水とアルコールとの混合物中、３−クロロ−２−ヒドロキシプロピルトリメチルアンモニウムクロリドおよび水酸化ナトリウムと反応させる工程、ｂ）水およびアルコールの量を、３０〜５０重量％の水を含有する６５〜９５重量％の水とアルコールとの混合物を含有する分散物を得るために調整し、分散物を、撹拌下、１５〜４０℃の温度で少なくとも１０分間維持する工程、ｃ）混合物を真空ろ過し、乾燥して精製カチオン性グアーを得る工程、を含む、０．０１〜３のＤＳを有するカチオン性グアーの調製手順である。 The basic object of the present invention is therefore the following steps: a) 100 parts by weight of guar powder in a mixture of 5 to 500 parts by weight of water and alcohol containing 20 to 50% by weight of water; Reacting with chloro-2-hydroxypropyltrimethylammonium chloride and sodium hydroxide, b) a mixture of 65 to 95% by weight of water and alcohol containing 30-50% by weight of water and alcohol. Adjusting the dispersion to obtain a dispersion containing, maintaining the dispersion at a temperature of 15-40 ° C. for at least 10 minutes with stirring, c) vacuum filtering the mixture and drying to obtain a purified cationic guar A process for preparing a cationic guar having a DS of 0.01 to 3.
本発明のために利用できるグアー粉は任意の市販のグアー粉であり、好ましくは最大１０重量％の水を含む。
本明細書中の表現「カチオン性グアー」は、グアー２−ヒドロキシ−３−（トリメチルアンモニウム）プロピルエーテルクロリドを意味する。
The guar powder that can be used for the present invention is any commercially available guar powder, preferably containing up to 10% by weight of water.
The expression “cationic guar” herein refers to guar 2-hydroxy-3- (trimethylammonium) propyl ether chloride.
０．０１〜３の置換度（ＤＳ）を有するカチオン性グアーを得るために、工程ａ）において、反応を、撹拌下、２〜６００重量部の３−クロロ−２−ヒドロキシプロピルトリメチルアンモニウムクロリドと、０．４〜１６０重量部の水酸化ナトリウム（または当量の他の強塩基）とを用いて行う。 In order to obtain a cationic guar having a degree of substitution (DS) of 0.01 to 3, in step a) the reaction is carried out with stirring with 2 to 600 parts by weight of 3-chloro-2-hydroxypropyltrimethylammonium chloride. , 0.4 to 160 parts by weight of sodium hydroxide (or equivalent amount of other strong base).
本明細書中、「置換度」（ＤＳ）なる表現は、１Ｈ−ＮＭＲによって測定されるグアーのヒドロキシル基に対するカチオン性基の置換を意味する。 In the present specification, the expression “degree of substitution” (DS) means the substitution of a cationic group with respect to the hydroxyl group of guar as measured by 1 H-NMR.
工程ｂ）において水およびアルコールの量を調整するには、水および／またはアルコールを加えるか、蒸留によって過剰な水およびアルコールを除去するか、または添加および蒸留の両方を行うことが可能であり、あるいは、何の添加も除去も必要としないこともある。 To adjust the amount of water and alcohol in step b), it is possible to add water and / or alcohol, remove excess water and alcohol by distillation, or both addition and distillation, Alternatively, no addition or removal may be required.
蒸留を避けるために、工程ａ）において、工程ｂ）の分散物に存在する量より少ないか、これと等しい量の水とアルコールとの混合物を用いるのが好ましい。
好ましくは、本手順の工程ａ）において、５０〜２００重量部の水とアルコールとの混合物を用いる。
In order to avoid distillation, it is preferred in step a) to use a mixture of water and alcohol in an amount less than or equal to the amount present in the dispersion of step b).
Preferably, in step a) of this procedure, a mixture of 50 to 200 parts by weight of water and alcohol is used.
本発明の好ましい実施形態によると、本反応の工程ａ）において、１０〜１００重量部の３−クロロ−２−ヒドロキシプロピルトリメチルアンモニウムクロリドと、２〜２７重量部の水酸化ナトリウムとを用い、調製の終わりに０．０５〜０．５のＤＳを有するカチオン性グアーを得る。この置換度は、最高のコンディショニング能を得ることを可能にする。 According to a preferred embodiment of the present invention, in step a) of this reaction, it is prepared using 10-100 parts by weight of 3-chloro-2-hydroxypropyltrimethylammonium chloride and 2-27 parts by weight of sodium hydroxide. A cationic guar having a DS of 0.05 to 0.5 is obtained at the end of. This degree of substitution makes it possible to obtain the highest conditioning capacity.
通常、当該技術分野でよく知られていることに従い、工程ａ）において、反応は４０〜８０℃の温度で０．５〜４時間行い、反応の終わりのｐＨを４〜１０に調整し、工程ｃ）の乾燥は、６０〜９０℃の温度で行い、ろ過の後、精製されたカチオン性グアーを粉砕する。
本発明の手順に有用なアルコールは、エタノール、イソプロパノールまたはこれらの混合物である。
Usually, in accordance with what is well known in the art, in step a) the reaction is carried out at a temperature of 40-80 ° C. for 0.5-4 hours, the pH at the end of the reaction is adjusted to 4-10, The drying of c) is performed at a temperature of 60 to 90 ° C., and after filtration, the purified cationic guar is pulverized.
Useful alcohols for the procedure of the present invention are ethanol, isopropanol or mixtures thereof.
特に有利な側面によると、本発明の手順は１回の洗浄および１回のろ過、ならびに、比較的少量の水およびアルコールの使用を含み、得られるカチオン性グアーは、ホウ素、有毒な溶媒、およびカテゴリーＣＭＲ１、ＣＭＲ２またはＣＭＲ３の、発がん性、変異原性または生殖毒性を有するものとして分類されている物質を含まない。 According to a particularly advantageous aspect, the procedure of the present invention comprises one wash and one filtration and the use of relatively small amounts of water and alcohol, the resulting cationic guar being boron, a toxic solvent, and Does not include substances classified as having carcinogenicity, mutagenicity, or reproductive toxicity of category CMR1, CMR2 or CMR3.
特に、本発明の手順によって得られる精製カチオン性グアーは、３−クロロ−２−ヒドロキシプロピルトリメチルアンモニウムクロリドを含まず、最小量の２，３−ジヒドロキシプロピルトリメチルアンモニウムクロリドを有する（カチオン化反応中、３−クロロ−２−ヒドロキシプロピルトリメチルアンモニウムクロリドと水との反応によって形成され得る）。 In particular, the purified cationic guar obtained by the procedure of the present invention is free of 3-chloro-2-hydroxypropyltrimethylammonium chloride and has a minimal amount of 2,3-dihydroxypropyltrimethylammonium chloride (during the cationization reaction, Formed by reaction of 3-chloro-2-hydroxypropyltrimethylammonium chloride with water).
本発明の手順の利点は、使用する水とアルコールとの混合物において生成物が完全に水に不溶性であるため、精製カチオン性グアーを高収率で得ることができることである。
記載された量の水およびアルコールの使用は、それが、カチオン性グアーの完全な不溶性を保証するほか、精製された生成物の取得をも可能にするので、この目的のために不可欠である。
An advantage of the procedure of the present invention is that the purified cationic guar can be obtained in high yield because the product is completely insoluble in the mixture of water and alcohol used.
The use of the stated amounts of water and alcohol is essential for this purpose, as it guarantees complete insolubility of the cationic guar and also allows the purification product to be obtained.
カチオン化試薬の残留物およびその関連するグリコールの決定は、カチオン***換カラムの使用およびメタンスルホン酸溶液での溶出によるイオン交換クロマトグラフィーによって行う。 The determination of the residue of the cationizing reagent and its associated glycol is performed by ion exchange chromatography using a cationic exchange column and elution with a methanesulfonic acid solution.
「３−クロロ−２−ヒドロキシプロピルトリメチルアンモニウムクロリドを含まない」なる表現は、本発明のカチオン性グアーにおいて、３−クロロ−２−ヒドロキシプロピルトリメチルアンモニウムクロリドの濃度が上述の方法の検出限界未満（この場合０．１５％未満）であることを意味する。 The expression “not containing 3-chloro-2-hydroxypropyltrimethylammonium chloride” means that in the cationic guar of the present invention, the concentration of 3-chloro-2-hydroxypropyltrimethylammonium chloride is below the detection limit of the above-described method ( In this case, it means less than 0.15%).
本発明の手順によって得られる生成物は、いずれのｐＨにおいても迅速かつ完全に溶解する。同生成物は、その正電荷を介して弱い陰電荷を有する基材に結合するその能力が、水溶液を増粘し、水溶液のレオロジーを調整するその能力と共に活用される種々の化粧用調合物に用いることができる。 The product obtained by the procedure of the present invention dissolves quickly and completely at any pH. The product can be used in a variety of cosmetic formulations where its ability to bind to a negatively charged substrate via its positive charge, along with its ability to thicken aqueous solutions and adjust the rheology of aqueous solutions. Can be used.
本発明の手順のさらなる利点は、そうして得たカチオン性グアーが、３重量％未満の無機塩（７００℃でのか焼により決定される量）、特に２重量％未満の塩化ナトリウムを含有することである。その存在は、よく知られているように、化粧品分野で一般的に用いられている増粘剤の効果に影響する。 A further advantage of the procedure according to the invention is that the cationic guar so obtained contains less than 3% by weight of inorganic salt (as determined by calcination at 700 ° C.), in particular less than 2% by weight of sodium chloride. That is. Its presence affects the effect of thickeners commonly used in the cosmetics field, as is well known.
本発明の手順において、粉の形態のグアーの使用が、本発明のカチオン性グアーに特有の純度特性を得るために重要であると考えられる。 In the procedure of the present invention, the use of guar in powder form is considered important to obtain the purity characteristics specific to the cationic guar of the present invention.
本発明のカチオン性グアーはまた、本生成物の純度特性が特に重要となる他の産業分野、例えばハウスケア、および皮膚と接触し得るすべての製品においても有用である。 The cationic guars of the present invention are also useful in other industries where the purity characteristics of the product are particularly important, such as house care and all products that can come into contact with the skin.
例１
５リットルの撹拌反応器に、８００ｇのグアー粉を室温で添加し、反応雰囲気を真空／窒素洗浄によって不活性化し、激しい撹拌下、４５０ｇの１／９の水／イソプロパノール溶液に溶解した５０ｇの水酸化ナトリウムを加える。撹拌を５０〜６０℃の温度で３０分間続ける。１００ｇの水に希釈した２２４ｇの３−クロロ−２−ヒドロキシプロピルトリメチルアンモニウムクロリド８５％を加える。同じ温度に２時間置いた後、反応物を４０℃に冷却し、ｐＨが約８になるまで二酸化炭素ガスを添加する。
Example 1
To a 5 liter stirred reactor, 800 g of guar powder was added at room temperature, the reaction atmosphere was deactivated by vacuum / nitrogen washing, and 50 g of water dissolved in 450 g of 1/9 water / isopropanol solution under vigorous stirring. Add sodium oxide. Stirring is continued for 30 minutes at a temperature of 50-60 ° C. Add 224 g 3-chloro-2-hydroxypropyltrimethylammonium chloride 85% diluted in 100 g water. After 2 hours at the same temperature, the reaction is cooled to 40 ° C. and carbon dioxide gas is added until the pH is about 8.
例２
例１に記載のとおりにして得た反応混合物を、撹拌下、８０００ｇの水とイソプロパノールとの混合物（６０重量％のアルコール）に分散し、得られた分散物を３０分間撹拌し、布フィルターで真空ろ過する（０．４〜０．５ａｔｍ）。
こうして得た精製カチオン性グアーを、水分含量が約３重量％になるまで流動床乾燥機で温風により乾燥し、粉砕し、分析する。
分析結果を表１に示す。
Example 2
The reaction mixture obtained as described in Example 1 is dispersed with stirring in a mixture of 8000 g of water and isopropanol (60% by weight alcohol), the resulting dispersion is stirred for 30 minutes and filtered with a cloth filter. Vacuum filter (0.4-0.5 atm).
The purified cationic guar thus obtained is dried with hot air in a fluid bed dryer until the water content is about 3% by weight, ground and analyzed.
The analysis results are shown in Table 1.
例３
例１に記載のとおりにして得た反応混合物を、撹拌下、８０００ｇの水とエタノールとの混合物（６０重量％）に分散し、得られた分散物を３０分間撹拌し、布フィルターで真空ろ過する（０．４〜０．５ａｔｍ）。
こうして得た精製カチオン性グアーを、水分含量が約３重量％になるまで流動床乾燥機で温風により乾燥し、粉砕し、分析する。
分析結果を表１に示す。
Example 3
The reaction mixture obtained as described in Example 1 is dispersed with stirring in a mixture of 8000 g of water and ethanol (60% by weight), the resulting dispersion is stirred for 30 minutes and vacuum filtered through a cloth filter. (0.4 to 0.5 atm).
The purified cationic guar thus obtained is dried with hot air in a fluid bed dryer until the water content is about 3% by weight, ground and analyzed.
The analysis results are shown in Table 1.
例４
例１に記載のとおりにして得た反応混合物を、撹拌下、８０００ｇの水とイソプロパノールとの混合物（６０重量％）に分散し、得られた分散物を３０分間撹拌し、布フィルターで真空ろ過する（０．４〜０．５ａｔｍ）。
こうして得た精製カチオン性グアーを、水分含量が約３重量％になるまで流動床乾燥機で温風により乾燥し、粉砕し、分析する。
分析結果を表１に示す。
Example 4
The reaction mixture obtained as described in Example 1 is dispersed with stirring in a mixture of 8000 g of water and isopropanol (60% by weight), the resulting dispersion is stirred for 30 minutes and vacuum filtered through a cloth filter. (0.4 to 0.5 atm).
The purified cationic guar thus obtained is dried with hot air in a fluid bed dryer until the water content is about 3% by weight, ground and analyzed.
The analysis results are shown in Table 1.
例５（比較）
例１に記載のとおりにして得た反応混合物を、撹拌下、８０００ｇの水とアセトンとの混合物（６０重量％のアセトン）に分散し、得られた分散物を３０分間撹拌し、布フィルターで真空ろ過する（０．４〜０．５ａｔｍ）。
こうして得たカチオン性グアーを、水分含量が約３重量％になるまで流動床乾燥機で温風により乾燥し、粉砕し、分析する。
分析結果を表１に示す。
Example 5 (comparison)
The reaction mixture obtained as described in Example 1 was dispersed with stirring in a mixture of 8000 g of water and acetone (60% by weight of acetone), and the resulting dispersion was stirred for 30 minutes and filtered with a cloth filter. Vacuum filter (0.4-0.5 atm).
The cationic guar thus obtained is dried with hot air in a fluid bed dryer until the water content is about 3% by weight, ground and analyzed.
The analysis results are shown in Table 1.
例６（比較）
例１に記載のとおりにして得た反応混合物を、撹拌下、８０００ｇの水とイソプロパノールとの混合物（９０重量％のアルコール）に分散し、得られた分散物を３０分間撹拌し、布フィルターで真空ろ過する（０．４〜０．５ａｔｍ）。
こうして得たカチオン性グアーを、水分含量が約３重量％になるまで流動床乾燥機で温風により乾燥し、粉砕し、分析する。
分析結果を表１に示す。
Example 6 (comparison)
The reaction mixture obtained as described in Example 1 is dispersed with stirring in a mixture of 8000 g of water and isopropanol (90% by weight alcohol), the resulting dispersion is stirred for 30 minutes and filtered with a cloth filter. Vacuum filter (0.4-0.5 atm).
The cationic guar thus obtained is dried with hot air in a fluid bed dryer until the water content is about 3% by weight, ground and analyzed.
The analysis results are shown in Table 1.
例７（比較）
例１に記載のとおりにして得た反応混合物を、撹拌下、２４００ｇの水とイソプロパノールとの混合物（６０重量％のアルコール）に分散し、得られた分散物を３０分間撹拌し、布フィルターで真空ろ過する（０．４〜０．５ａｔｍ）。
そうして得たカチオン性グアーを、水分含量が約３重量％になるまで流動床乾燥機で温風により乾燥し、粉砕し、分析する。
分析結果を表１に示す。
Example 7 (comparison)
The reaction mixture obtained as described in Example 1 is dispersed with stirring in 2400 g of a mixture of water and isopropanol (60% by weight alcohol), the resulting dispersion is stirred for 30 minutes and filtered with a cloth filter. Vacuum filter (0.4-0.5 atm).
The cationic guar thus obtained is dried with hot air in a fluid bed dryer until the water content is about 3% by weight, ground and analyzed.
The analysis results are shown in Table 1.
Claims (5)
ａ）１００重量部のグアー粉を、２０〜５０重量％の水を含有する５〜５００重量部の水とアルコールとの混合物中、３−クロロ−２−ヒドロキシプロピルトリメチルアンモニウムクロリドおよび水酸化ナトリウムと反応させる工程、
ｂ）水およびアルコールの量を、３０〜５０重量％の水を含有する水とアルコールとの混合物を６５〜９５重量％含有する分散物を得るために調整し、分散物を撹拌下、１５〜４０℃の温度で少なくとも１０分間維持する工程、
ｃ）混合物を真空ろ過し、乾燥して精製カチオン性グアーを得る工程、
を含み、前記アルコールがエタノール、イソプロパノールまたはこれらの混合物である、０．０１〜３のＤＳを有するカチオン性グアーを調製するための手順。 The following steps:
a) 100 parts by weight of guar powder with 3-chloro-2-hydroxypropyltrimethylammonium chloride and sodium hydroxide in a mixture of 5 to 500 parts by weight of water and alcohol containing 20 to 50% by weight of water Reacting,
b) the amount of water and alcohol, to adjust the mixture of water and alcohol you containing 30 to 50 wt% of water to obtain a dispersion containing 65 to 95 wt%, under stirring of the dispersion, 15 Maintaining at a temperature of ˜40 ° C. for at least 10 minutes;
c) vacuum filtering the mixture and drying to obtain purified cationic guar;
Only contains the the alcohol is ethanol, isopropanol or mixtures thereof, procedures for the preparation of cationic guar having a DS of 0.01 to 3.
The procedure according to any one of claims 1 to 4 , wherein after the filtration, the purified cationic guar is pulverized.
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| ITVA2006A000069 | 2006-11-17 | ||
| IT000069A ITVA20060069A1 (en) | 2006-11-17 | 2006-11-17 | PROCEDURE FOR THE PREPARATION OF PURIFIED CATIONIC GUAR |
| PCT/EP2007/053710 WO2008058769A1 (en) | 2006-11-17 | 2007-04-17 | Procedure for the preparation of purified cationic guar |
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| CN101735332B (en) * | 2010-01-14 | 2012-12-26 | 淮南华俊新材料科技有限公司 | Cation guar gum and production method thereof |
| CN101974100B (en) * | 2010-11-22 | 2012-05-30 | 沈阳工业大学 | Composite modified guar and preparation method thereof |
| WO2012071056A2 (en) * | 2010-11-23 | 2012-05-31 | Rhodia Operations | Guar process monitoring methods |
| CN102887959A (en) * | 2011-07-19 | 2013-01-23 | 黎川县川盛实业有限公司 | Method for synthesizing cationic guar gum by mixed solvent method |
| FR2980795B1 (en) * | 2011-10-03 | 2014-02-28 | Rhodia Operations | PROCESS FOR THE PREPARATION OF CATIONIC GALACTOMANNANES |
| ITVA20130041A1 (en) * | 2013-07-24 | 2015-01-25 | Lamberti Spa | GALATTOMANNANI CATIONIC |
| ITVA20130048A1 (en) | 2013-09-04 | 2015-03-05 | Lamberti Spa | COSMETIC COMPOSITIONS AND FOR THE CARE OF THE HOUSE |
| CN103524634A (en) * | 2013-09-28 | 2014-01-22 | 昆山市周市溴化锂溶液厂 | Preparation method for guar gum for fabric caring |
| US10301531B2 (en) | 2015-07-23 | 2019-05-28 | Uniquem Inc. | Modified natural polymers as bitumen encapsulants |
| JP7206199B2 (en) * | 2016-09-16 | 2023-01-17 | アケリオス・セラピューティクス・インコーポレーテッド | topical anti-inflammatory composition |
| EP3687309B1 (en) * | 2017-09-28 | 2024-02-14 | Specialty Operations France | Process for drying polysaccharides |
| CN114149513B (en) * | 2021-12-27 | 2022-10-11 | 昆山京昆油田化学科技有限公司 | Carboxymethyl dihydroxypropyl modified guar gum and preparation method and application thereof |
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| US3912713A (en) * | 1973-08-29 | 1975-10-14 | Scholten Honig Research Nv | Guar gum derivatives and process for preparation |
| US4031307A (en) | 1976-05-03 | 1977-06-21 | Celanese Corporation | Cationic polygalactomannan compositions |
| US4061602A (en) | 1976-08-03 | 1977-12-06 | American Cyanamid Company | Conditioning shampoo composition containing a cationic derivative of a natural gum (such as guar) as the active conditioning ingredient |
| US4959464A (en) | 1988-11-07 | 1990-09-25 | Hi-Tek Polymers, Inc. | Process for derivatizing polygalactomannan using water soluble aluminum salts in the process |
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| EP0884330A1 (en) * | 1997-06-12 | 1998-12-16 | Meyhall AG | Process for producing pure guar seed flour |
| AU2122999A (en) * | 1998-03-18 | 1999-09-30 | National Starch And Chemical Investment Holding Corporation | Method for preparation of amphoteric guar gum derivatives |
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